Nitro- or cyano-derivatives of 2-imino-imidazolines and 2-imino-tetrahydropyrimidines

ABSTRACT

Novel intermediates for insecticides of the formula (I) ##STR1## wherein Y represents nitro or cyano; 
     A represents an ethylene or trimethylene radical, which is optionally substituted; and 
     Z can have many possible meanings.

The present invention relates to novel nitro- or cyanoimino compounds and to processes for their preparation.

It has already been disclosed that certain cyanoimino compounds are useful as intermediates for active compounds such as insecticides, anti-diabetic agents, virus-suppressing agents and diuretic agents (see Japanese patent Laid-open 91,064/1983).

Furthermore, certain nitroimino compounds have been disclosed in Can. J. Chem., Vol. 39, pp. 1787 to 1796.

There have now been found novel-nitro- or cyano derivatives of 2-imino-imidazolidines and 2-imino-tetrahydropyrimidines of the general formula (I): ##STR2## wherein Y represents nitro or cyano;

A represents an ethylene or trimethylene radical, which is optionally mono- or poly-substituted (e.g. di- or tri-substituted) with one or more radicals selected, for instance, from the class consisting of halogen and alkyl with 1 to 4 carbon atoms;

Z represents cycloalkyl with 3 to 7 carbon atoms (which is optionally substituted with methyl);

haloalkyl with 1 to 4 carbon atoms;

alkoxyalkyl having 2 to 6 carbon atoms in total;

alkylthioalkyl having 2 to 6 carbon atoms in total;

alkylsulfinylalkyl having 2 to 6 carbon atoms in total;

alkylsulfonylalkyl having 2 to 6 carbon atoms in total;

alkyl having 1 to 3 carbon atoms and carrying one or more substituents (which substituents are selected, for instance, from the class consisting of optionally substituted phenoxy, optionally substituted phenylthio, optionally substituted pyridyloxy, optionally substituted cycloalkyl having 3 to 6 carbon atoms, optionally substituted pyridylthio, thiazolylthio, benzyloxy, thiocyanato, dialkylamino having 2 to 6 carbon atoms in total, alkoxy-alkoxy having 2 to 4 carbon atoms in total, optionally substituted anilino, optionally substituted pyridylamino, cyano, alkylcarbonyl having an alkyl moiety with 2 to 4 carbon atoms, optionally substituted benzoyl, haloalkylcarbonyl with a haloalkyl moiety having 1 to 3 carbon atoms, pyridylcarbonyl, alkoxycarbonyl having an alkyl moiety with 1 to 4 carbon atoms, optionally substituted phenoxycarbonyl, benzyloxycarbonyl, carbamoyl, alkylaminocarbonyl with 1 to 3 carbon atoms, dialkylaminocarbonyl having 2 to 6 carbon atoms in total, optionally substituted phenylaminocarbonyl, hydroxy, alkylcarbonyloxy with 1 to 3 carbon atoms (which is optionally substituted with halogen), benzoyloxy, alkylsulfonyloxy with 1 to 4 carbon atoms, tosyloxy, dialkylaminocarbonyloxy having an alkyl moiety with 1 to 3 carbon atoms, a phosphate ester radical, a thiophosphate ester radical, an amidothiophosphate radical, trimethylsilyl, an optionally substituted 9- or 10-membered condensed heterocyclic radical having at least one hetero-atom selected from the group consisting of N, O and S);

phenyl (which may optionally carry one or more substituents selected, for instance, from the class consisting of halogen, alkyl with 1 to 3 carbon atoms, and nitro);

a 5- or 6-membered heterocyclic or 9- or 10-membered condensed heterocyclic radical having at least one hetero-atom selected from the group consisting of N, O and S (which is optionally substituted with a radical as in the above phenyl group);

alkenyl having 3 to 4 carbon atoms optionally substituted with halogen;

propargyl optionally substituted with halogen;

alkoxyl with 1 to 4 carbon atoms; cyano; phenoxy; benzyloxy; alkenyloxy with 2 or 3 carbon atoms;

alkylthio with 1 to 4 carbon atoms optionally substituted with halogen;

phenylthio optionally substituted with halogen and/or alkyl having 1 to 4 carbon atoms;

halobenzylthio; dialkylamino having 2 to 6 carbon atoms in total;

alkylcarbonyl having an alkyl moiety with 2 to 6 carbon atoms;

alkylcarbonyl having an alkyl moiety with 1 to 4 carbon atoms having a substituent (which is selected, for instance, from the group consisting of halogen, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkylcarbonyloxy having an alkyl moiety with 1 to 4 carbon atoms, halophenoxy, phenyl, cyano, and alkylcarbonyl having an alkyl moiety with 1 to 2 carbon atoms);

cycloalkylcarbonyl with 3 to 6 carbon atoms optionally substituted with halogen and/or with alkyl having 1 to 4 carbon atoms;

benzoyl (which may be optionally substituted, for instance, with a radical selected from the group consisting of halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, nitro, haloalkyl with 1 to 4 carbon atoms, alkylcarbonylamino having an alkyl moiety with 1 to 4 carbon atoms, and alkoxy-alkoxy having 2 to 4 carbon atoms in total);

alkenylcarbonyl having an alkenyl moiety with 2 to 4 carbon atoms optionally substituted with halogen;

alkynylcarbonyl having an alkynyl moiety with 2 to 3 carbon atoms;

a radical of the formula: ##STR3## (wherein U² represents a 5- or 6-membered heterocyclic or 9- or 10-membered condensed heterocyclic radical having at least one hetero-atom selected from the group consisting of N, O and S (which heterocyclic radical may optionally carry one or more substituents selected, for example, from the group consisting of halogen, alkyl with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms, phenyl, nitro, alkylthio with 1 to 4 carbon atoms, and oxo);

alkoxycarbonyl having an alkyl moiety with 1 to 3 carbon atoms substituted with a radical (which substituent is selected, for instance, from the group consisting of halogen, alkoxy with 1 or 2 carbon atoms, alkylthio with 1 to 2 carbon atoms, dialkylamino having 2 to 4 carbon atoms in total, hydroxy, and halophenoxy);

cycloalkoxycarbonyl having a cycloalkyl moiety with 3 to 7 carbon atoms (which may be optionally substituted with alkyl having 1 to 4 carbon atoms);

phenoxycarbonyl substituted with a radical (which substituent is selected, for instance, from the group consisting of halogen, alkyl with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms, cyano, alkylthio with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, nitro, alkylsulfinyl with 1 to 4 carbon atoms, alkoxycarbonyl having an alkyl moiety with 1 to 4 carbon atoms, and pyridyloxy substituted with halogen and/or with trihaloalkyl);

benzyloxycarbonyl optionally substituted with a radical (which substituent is selected, for instance, from the class consisting of halogen, haloalkyl with 1 to 2 carbon atoms, alkoxy with 1 to 4 carbon atoms, and phenoxy);

phenylthiocarbonyl; alkylthiocarbonyl having an alkyl moiety with 1 to 4 carbon atoms; alkenyloxycarbonyl having an alkenyl moiety with 2 to 4 carbon atoms optionally substituted with halogen; alkynyloxycarbonyl having an alkynyl moiety with 2 to 4 carbon atoms optionally substituted with halogen;

a radical of the formula: ##STR4##

(wherein Q¹ represents a 5- or 6-membered heterocyclic or 9- or 10-membered condensed heterocyclic radical having at least one hetero-atom selected from the group consisting of N, O and S, which is optionally substituted with a radical selected, for instance, from the group consisting of halogen, alkyl with 1 to 4 carbon atoms, phenyl, oxo and haloalkyl with 1 to 4 carbon atoms);

carbomoyl; alkylaminocarbonyl having an alkyl moiety with 1 to 4 carbon atoms; cycloalkylaminocarbonyl having a cycloalkyl moiety with 3 to 6 carbon atoms;

phenylaminocarbonyl (which may be optionally substituted with a radical selected, for example, from the group consisting of halogen, alkyl with 1 to 4 carbon atoms, and alkoxy with 1 to 4 carbon atoms);

dialkylaminocarbonyl having alkyl moieties with 2 to 8 carbon atoms in total;

a radical of the formula: ##STR5## (wherein G represents a 5- or 6-membered heterocyclic or 9- or 10-membered condensed heterocyclic radical having at least one hetero-atom selected from the class consisting of N, O and S, which is optionally substituted with a radical selected, for instance, from the group consisting of halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms, and alkylsulfonyl with 1 or 2 carbon atoms;

n is 0 or 1; and

R' represents hydrogen or alkyl with 1 to 4 carbon atoms);

piperidinocarbonyl which is optionally substituted, for instance, with alkyl having 1 to 4 carbon atoms;

morpholinocarbonyl which is optionally substituted, for instance, with alkyl having 1 to 4 carbon atoms;

pyrrolidinocarbonyl;

benzylaminocarbonyl optionally substituted with methyl;

mono- or di-alkenylaminocarbonyl having one or two alkenyl moieties with 2 to 3 carbon atoms;

alkynylamino-carbonyl with a alkynyl moiety having 2 to 3 carbon atoms;

alkylsulfonyl with 1 to 4 carbon atoms (which radical may be optionally substituted with halogen);

phenylsulfonyl (which may be optionally substituted with a radical selected, for instance, from the group consisting of halogen, alkyl with 1 to 4 carbon atoms, and nitro);

alkoxysulfonyl with 1 to 4 carbon atoms;

cycloalkoxysulfonyl with 3 to 6 carbon atoms;

mono- or di-(C₁₋₄ alkyl)-aminosulfonyl;

phenylaminocarbonyl (which may be optionally substituted with methyl);

O,O-di-(C₁₋₄ alkyl)-phosphono;

O,O-di-(C₁₋₄ alkyl)-thiophosphono;

O,S-di-(C₁₋₄ alkyl)-thiophosphono;

O-(C₁₋₄ alkyl)-O-(phenyl optionally substituted with halogen)thiophosphono;

O,N-di-(C₁₋₄ alkyl)-amidothiophosphono;

alkoxalyl with 1 to 4 carbon atoms;

phenoxalyl optionally substituted with halogen;

benzyloxalyl; or

a radical of the formula ##STR6## wherein Y and A have the meanings stated above, and T represents --S--, --S--S--, ##STR7##

The compounds of the formula (I) are obtained by a process in which,

(a) compounds of the formula (II) ##STR8## wherein Y and A have the meanings stated above, are reacted with compounds of the formula (III)

    Z--M.sup.1                                                 (III)

wherein Z has the meaning stated above, and M¹ represents halogen, preferably chlorine or bromine, in the presence of an inert solvent and if appropriate in the presence of a base,

or

(b) compounds of the formula (IV)

    H.sub.2 N--A--NH--Z                                        (IV)

wherein A and Z have the meanings stated above, are reacted with compounds of the formula (V) ##STR9## wherein Y has the meaning stated above, and M² represents amino, alkylthio or benzylthio, in the presence of an inert solvent, or

(c) in the case where Y is cyano:

compounds of the aforesaid formula (IV) are reacted with compounds of the formula (IV)

    (M.sup.3 --S).sub.2 C═N--CN                            (VI)

wherein M³ represents alkylthio or benzylthio, with the proviso that the two radicals M³ together with the sulfur atoms, may form a ring, in the presence of an inert solvent.

The novel nitro- or cyano imino compounds are very useful as intermediates for certain insecticidal nitro- or cyano-imino compounds as stated in detail hereinafter.

Among the compounds of the formula (I) according to the invention, of the formula (I), preferred compounds are those in which

Y represents nitro or cyano;

A represents an ethylene or trimethylene radical, which may optionally mono- or di-substituted (e.g. di- or tri-substituted) with chlorine or methyl;

Z represents cycloalkyl with 5 to 6 carbon atoms (which is optionally substituted with methyl);

haloalkyl with 1 to 3 carbon atoms;

alkoxyalkyl having 2 to 4 carbon atoms in total;

alkylthioalkyl having 2 to 4 carbon atoms in total;

alkylsulfinylalkyl having 2 to 4 carbon atoms in total;

alkylsulfonylalkyl having 2 to 4 carbon atoms in total;

alkyl having 1 to 3 carbon atoms and carrying one or more substituents [(which substituents are selected from phenoxy optionally substituted with at least one member selected from halogen, nitro, alkyl with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms and haloalkoxy with 1 to 4 carbon atoms);

phenylthio optionally substituted with at least one radical such as shown in the above phenoxy group; pyridylthio optionally substituted with a halogen;

cycloalkyl with 3 to 7 carbon atoms optionally substituted with chlorine and/or methyl; pyridylthio optionally substituted with a halogen;

thiazolylthio; benzyloxy; thiocyanato; dialkylamino having 2 to 4 carbon atoms in total; alkoxy-alkoxy having 2 to 3 carbon atoms in total;

anilino optionally substituted with at least one radical selected from halogen and alkyl with 1 to 4 carbon atoms; pyridylamino optionally substituted with at least one radical such as shown in the above anilino group; cyano;

alkylcarbonyl having an alkyl moiety with 2 to 3 carbon atoms;

benzoyl optionally substituted with a halogen; haloalkylcarbonyl with a haloalkyl moiety having 1 to 2 carbon atoms;

pyridylcarbonyl; alkoxycarbonyl having an alkyl moiety with 1 to 2 carbon atoms;

phenoxycarbonyl optionally substituted with at least one radical selected from halogen and alkyl with 1 to 4 carbon atoms; benzyloxycarbonyl; carbamoyl; alkylaminocarbonyl having an alkyl moiety with 1 to 2 carbon atoms; dialkylaminocarbonyl having an alkyl moiety with 2 to 4 carbon atoms in total; phenylaminocarbonyl; hydroxy; alkylcarbonyloxy with 1 to 2 carbon atoms (which may be optionally substituted with halogen); benzoyloxy; alkylsulfonyloxy with 1 to 2 carbon atoms; tosyloxy; dialkylaminocarbonyloxy having an alkyl moiety with 2 to 4 carbon atoms in total;

O,O-dialkylphosphono with 2 to 6 carbon atoms in total;

O,O-dialkylthiophosphorylthio with 2 to 6 carbon atoms in total;

O,S-dialkylthiophosphoryloxy with 2 to 6 carbon atoms in total;

trimethylsilyl; and a 9- or 10-membered condensed heterocyclic radical with at least one hetero-atom selected from the class consisting of N,O and S (which may be optionally substituted with at least one radical selected from halogen, alkyl with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms, phenyl, nitroimino, cyanoimino, oxo, alkylthio with 1 to 4 carbon atoms, and alkoxy with 1 to 4 carbon atoms)];

phenyl (which may optionally carry at least one substituents selected from fluorine, chlorine, bromine methyl, ethyl and nitro);

a 5- or 6-membered heterocyclic or 9- or 10-membered condensed heterocyclic radical having at least one hetero-atom selected from the group consisting of N, O and S (which may be optionally substituted with at least one radical such as shown in the above phenyl group);

alkenyl having 3 to 4 carbon atoms optionally substituted with chlorine;

propargyl optionally substituted with chlorine;

alkoxy with 1 to 4 carbon atoms; cyano; phenoxy; benzyloxy;

vinyloxy; allyloxy;

alkylthio with 1 to 3 carbon atoms optionally substituted with fluorine or chlorine;

phenylthio optionally substituted with at least one radical selected from fluorine, chlorine, methyl and ethyl;

halobenzylthio; dialkylamino having 2 to 4 carbon atoms in total;

alkylcarbonyl having an alkyl moiety with 2 to 4 carbon atoms;

alkylcarbonyl having an alkyl moiety with 1 to 2 carbon atoms having a substituent (which is selected from halogen, alkoxy with 1 to 3 carbon atoms, alkylthio with 1 to 3 carbon atoms, alkylcarbonyloxy having an alkyl moiety with 1 to 3 carbon atoms, halophenoxy, phenyl, cyano, and acetyl);

cycloalkylcarbonyl with 5 to 6 carbon atoms optionally substituted with chlorine and/or methyl;

benzoyl (which may be optionally substituted with at least one radical selected from halogen, alkyl with 1 to 3 carbon atoms, alkoxy with 1 to 3 carbon atoms, nitro, haloalkyl with 1 to 3 carbon atoms, alkylcarbonylamino having an alkyl moiety with 1 to 3 carbon atoms, and alkoxy-alkoxy having 2 to 3 carbon atoms in total);

alkenylcarbonyl having an alkenyl moiety with 2 to 3 carbon atoms optionally substituted with fluorine or chlorine; propargylcarbonyl;

a radical of the formula: ##STR10## (wherein U² represents a 5- or 6-membered heterocyclic or 9- or 10-membered condensed heterocyclic radical having at least one hetero-atom selected from the group consisting of N, O and S (which heterocyclic radical may optionally carry at least one substituent selected, from fluorine, chlorine, methyl, ethyl, haloalkyl with 1 to 2 carbon atoms, phenyl, nitro, alkylthio with 1 to 2 carbon atoms, and oxo);

alkoxycarbonyl having an alkyl moiety with 1 to 2 carbon atoms substituted with at least one substituent selected from fluorine, chlorine,

methoxy, ethylthio, diethylamino, hydroxy and chlorophenoxy;

cycloalkoxycarbonyl having a cycloalkyl moiety with 5 to 6 carbon atoms (which may be optionally substituted with methyl);

phenoxycarbonyl substituted with a radical (which substituent is selected from chlorine, methyl, trifluoromethyl, cyano, methylthio, methoxy, nitro, alkoxycarbonyl having an alkyl moiety with 1 to 3 carbon atoms, and pyridyloxy substituted with chlorine and/or trifluoromethyl);

benzyloxycarbonyl optionally substituted with a radical (which substituent is selected from chlorine, trifluoromethyl, methoxy and phenoxy);

phenylthiocarbonyl; ethylthiocarbonyl; alkenyloxycarbonyl having an alkenyl moiety with 2 to 3 carbon atoms optionally substituted with chlorine; propargyloxycarbonyl optionally substituted with halogen;

a radical of the formula: ##STR11## (wherein Q¹ represents a 5- or 6-membered heterocyclic or 9- or 10-membered condensed heterocyclic radical having at least one hetero-atom selected from the group consisting of N, O and S, which may be optionally substituted with a radical selected from chlorine, alkyl with 1 to 3 carbon atoms, phenyl, oxo and trifluoromethyl);

carbamoyl; alkylaminocarbonyl having an alkyl moiety with 1 to 3 carbon atoms; cyclohexylaminocarbonyl;

phenylaminocarbonyl (which is optionally substituted with a radical selected from chlorine, methyl, ethyl, and alkoxy with 1 to 3 carbon atoms);

dialkylaminocarbonyl having alkyl moieties with 2 to 4 carbon atoms in total;

a radical of the formula: ##STR12## (wherein G represents a 5- or 6-membered heterocyclic or 9-or 10-membered condensed heterocyclic radical having at least one hetero-atom selected from the class consisting of N, O and S, which may be optionally substituted with a radical selected from fluorine, chlorine, alkyl with 1 to 3 carbon atoms, methoxy, trifluoromethyl, and ethylsulfonyl;

n is 0 or 1; and

R¹ represents hydrogen or alkyl with 1 to 3 carbon atoms);

piperidinocarbonyl which may be optionally substituted with methyl;

morpholinocarbonyl which may be optionally substituted with methyl;

pyrrolidinocarbonyl;

benzylaminocarbonyl optionally substituted with methyl; mono- or di-allylaminocarbonyl;

propargylaminocarbonyl;

alkylsulfonyl with 1 to 4 carbon atoms (which may be optionally substituted with chlorine or fluorine);

phenylsulfonyl (which may be optionally substituted with a radical selected from chlorine, methyl and nitro);

methoxysulfonyl;

cyclohexyloxy sulfonyl with 3 to 6 carbon atoms;

mono- or di-(C₁₋₃ alkyl)-aminosulfonyl;

phenylaminocarbonyl;

O,O-di-(C₁₋₃ alkyl)-phosphono;

O,O-di-(C₁₋₃ alkyl)-thiophosphono;

O,S-di-(C₁₋₃ alkyl)-thiophosphono;

O-(C₁₋₂ alkyl)-O-(phenyl optionally substituted with chlorine)thiophosphono;

O,N-di-(C₁₋₃ alkyl)-amidothiophosphono;

alkoxalyl with 1 to 2 carbon atoms;

phenoxalyl optionally substituted with chlorine)benzyloxalyl; or

a radical of the formula ##STR13## wherein Y and A have the same preferred meanings stated above, and T represents --S--, --S--S--, ##STR14##

Specifically, the following compounds may be mentioned:

1-cyclopropyl-2-nitroiminoimidazolidine,

1-(2-chloroethyl)-2-nitroiminoimidazolidine,

1-[2-(4-chlorophenoxy)ethyl]-2-nitroiminoimidazolidine,

1-(3-methylthiopropyl)-2-nitroiminoimidazolidine,

1-(2-cyanoethyl)-2-nitroiminoimidazolidine,

1-(3-cyanopropyl)-2-cyanoiminoimidazolidine,

1-(3,3-dimethyl-2-butanon-1-yl)-2-cyanoiminoimidazolidine,

1-(3,3-dimethyl-2-butanon-1-yl)-2-nitroiminoimidazolidine,

2-nitroimino-1-(3-pyridylcarbonylmethyl)imidazolidine,

2-cyanoimino-1-ethoxycarbonylmethyltetrahydropyrimidine,

1(2-hydroxyethyl)-2-nitroiminoimidazolidine,

1-[2-(O-ethyl-S-propylthiophosphonoxy)ethyl]-2-nitroiminoimidazolidine,

2-nitroimino-1-trimethylsilylmethylimidazolidine,

1-(4nitrophenyl)-2-nitroiminoimidazolidine,

2-nitroimino-1-(2-thiazolyl)imidazolidine,

2-nitroimino-1-propylcarbonylimidazolidine,

2-cyanoimino-1-cyclopropylcarbonyltetrahydropyrimidine,

1-bromoacetyl-2-nitroiminoimidazolidine,

2-cyanoimino-1-trichloroacryloylimidazolidine,

1-(2-methoxyethoxycarbonyl)-2-nitroiminoimidazolidine,

1-benzyloxycarbonyl-2-nitroiminoimidazolidine,

1-ethylaminocarbonyl-2-nitroiminoimidazolidine,

1-dimethylaminocarbonyl-2-nitroiminoimidazolidine,

1-methylsulfonyl-2-nitroiminoimidazolidine,

2-nitroimino-1-phenylsulfonyltetrahydropyrimidine,

1-(O,O-dimethylphosphono)-2-nitroiminoimidazolidine,

1-(O-ethyl-S-propylthiophosphono)-2-nitroiminoimidazolidine,

1-(2,4-dichlorobenzoyl)-2-nitroiminoimidazolidine,

1-(3,5-dichlorobenzoyl)-2-cyanoiminoimidazolidine,

1-(2-furoyl)-2-nitroiminoimidazolidine,

If, for example in the process (a), 2-nitroiminoimidazolidine and 1-chloro-3,3-dimethyl-2-butanone are used as starting materials, the course of the reaction can be represented by the following equation: ##STR15## If, for example in the process (b), N-allylethylenediamine and N-nitro S-methylisothiourea are used as starting material, the course of the reaction can be represented by the following equation: ##STR16##

If, for example in the process (c), N-2-phenoxy-ethylethylenediamine and dimethyl N-cyanodithioiminocarbonate are used as starting materials, the course of the reaction can be represented by the following equation: ##STR17##

In the process (a), the compounds of the formula (II) as starting materials means those, based on the aforementioned definitions of Y and A.

In the formula (II), Y and A preferably have the meaning already given above.

The compounds of the formula (II) include known ones and are, for instance, described in J. Am. Chem. Soc., Vol. 73, pp. 2201 to 2205, and British Pat. No. 2,055,796.

In the process (a), the compounds of the formula (III) mean those, based on the aforementioned definitions of Z and M¹.

In the formula (III), Z and M¹ preferably have the meanings already given above.

The compounds of the formula (III) are well known in the field of organic chemistry.

In the process (b), the compounds of the formula (IV) as starting materials mean those based on the aforementioned definitions of A and Z.

In the formula (IV), A and Z preferably have the meanings already given above.

The compounds of the formula (IV) include known ones and in general, are easily obtained when compounds of the formula (VII)

    H.sub.2 N--A--NH.sub.2                                     (VII)

wherein A has the meaning stated above,

are reacted with the compounds of the aforementioned formula (III) in the presence of an inert solvent and if appropriate in the presence of a base.

The compounds of the above formula (VII) are known.

As examples there may be mentioned: ethylenediamine and trimethylenediamine, described in German Offenlegungsschrift No. 2,732,660 or French Pat. No. 1,499,785.

In the process (b), the compounds of the formula (V) also used as starting materials are known (for instance, see J. Am. Chem. Soc., Vol. 76, p. 1877)

In the process (c), the compounds of the formula (VI) as materials are known from J. Org. Chem., Vo. 32, pp. 1566-1572.

The process (a) according to the invention may be carried out using a suitable solvent or diluent. Virtually any inert organic solvent can be used as the solvent or diluent. Examples of the solvents or diluents are water; aliphatic, cycloaliphatic and aromatic, optionally chlorinated, hydrocarbons, such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, trichloroethylene, chlorobenzene and the like; ethers such as diethyl ether, methyl ethyl ether, di-isopropyl ether, dibutyl ether, propylene oxide, dioxane, tetrahydrofuran and the like; nitriles such as acetonitrile, propionitrile, acrylonitrile and the like; alcohols such as methanol, ethanol, iso-propanol, butanol, ethylene glycol and the like; acid amides such as dimethyl formamide, dimethyl acetamide and the like; and sulfones and sulfoxides such as dimethyl sulfoxide, sulfolane and the like.

The process (a) according to the invention may be conduct in the presence of a base such as alkali metal hydroxides or carbonates, for instance, sodium hydroxide, potassium hydroxide or the like.

The reaction temperature can be varied within a wide range. In general, the reaction is carried out at a temperature of about 0° to 100° C., preferably about 10° to 80° C.

In general, the reaction is allowed to proceed under normal pressure, although it is also possible to employ a higher or lower pressure.

When the process (a) is carried out in an inert solvent to prepare the compounds of the formula (I), it is possible to use about 0.9 to 1.1 moles of the compounds (II) per 1 mole of the compounds (II) in the presence of a base.

In carrying out the processes (b) and (c), suitable diluents include the same solvents as exemplified for process (a).

Process (b) can generally be conducted at a temperature of about 0° to 120° C., preferably about 30° to 100° C. It is advantageous to carry out the process (b) under normal pressure, although it is also possible to conduct this process under higher or lower pressure.

When the process (b) is carried out to obtain the compounds of the formula (I), generally about 1 to 1.2 moles, preferably about 1 to 1.1 moles of the compounds (V) are used per 1 mole of the compounds (IV). In the process (b), the compounds (IV) and the compounds (V) may be heated, for example, in water to react them with each other.

The process (c) can be carried out, for instance, at a temperature of about 0° C. to the boiling point of the reaction mixture, preferably at a temperature of about 0° to 100° C. It is generally advantageous to conduct the reaction under normal pressure, although a higher or lower pressure may also be employed.

When the process (c) is conducted to obtain the compounds (I), use is made of about 1 to 1.2 moles, preferably about 1 to 1.1 moles of the compounds (VI) per 1 mole of the compounds (IV). This reaction should preferably be conducted in an inert solvent such as an alcohol, e.g. methanol or ethanol until the evolution of mercaptants has ceased.

The compounds of the following formula (E) which can be prepared by using the compounds of the formula (I) as intermediates exhibit strong insecticidal action: ##STR18## wherein Y, A and Z have the same meanings as stated above, and R represents hydrogen or alkyl, and W represents an optionally substituted 5 or 6-membered heterocyclic radical having at least one hetero-atom and selected from the class consisting of N, O and S.

The preparation of products having formula (E) can be illustrated as follows: ##STR19## In the above formulae Y, A, Z, W, R have the meanings indicated above and Hal stands for a halogen atom.

The compounds of the above formula (E) can be obtained, for example, in accordance with Referential examples 1 and 2 as specified hereinafter.

Furthermore, the compounds of the formula (I) per se also exhibit an insecticidal action.

The invention is illustrated in detail by the following nonlimiting Examples.

Preparative Examples Example 1 ##STR20##

A mixture of 2.6 g of 2-nitroimino-imidazolidine, 3.0 g of anhydrous potassium carbonate and 30 ml of dry acetonitrile was stirred at room temperature for 30 minutes. Then, 2.7 g of 1-chloro-3,3-dimethyl-2-butanone were added to the mixture under stirring at room temperature. The reaction mixture was heated and refluxed for 1 hour. The acetonitrile was distilled off under a reduced pressure, and the residue was admixed with water. The aimed product was separated by filtration. The crystalline product was washed in ether and dried. 3.5 g of 1-(3,3-dimethyl-2-butanon-1-yl)-2-nitroimino-imidazolidine were obtained. mp. 158°-159° C.

Example 2 ##STR21##

2.2 g of 2-cyanoimino-imidazolidine is dissolved in 20 ml of dry dimethyl formamide. To this solution were portionwise added 1.7 g of 60% oil dispersed sodium hydride at a temperature of at most 0° C. The reaction mixture was stirred at 0° C. until the evolution of hydrogen had ceased. To the reaction mixture were dropwise added 1.9 g of propionyl chloride while the reaction mixture was kept at a temperature lower than 0° C. After this addition, the reaction mixture was stirred at room temperature for a short period of time. The reaction mixture was poured into ice water, and neutralized with hydrochloric acid. An extraction operation was carried out by using dichloromethane, and the extractant was concentrated, so that the aimed product was precipitated as a crystalline material. The precipitated product was separated by filtration, and washed in ether, 1.4 g of 2-cyanoimino-1-propionyl-imidazolidine were obtained. mp. 208°-210° C.

Example 3 ##STR22##

To a solution of 2.6 g of 2-nitroimino-imidazolidine in 20 ml of dimethyl formamide was portionwise added 0.8 g of 60% oil dispersed sodium hydride at room temperature. The reaction mixture was then stirred, until the evolution of hydrogen has ceased. Then, 3.6 g of 2,3,5-trichloropyridine were added, and the reaction mixture was stirred at a temperature of 100° to 120° C. for 7 hours. The reaction was cooled to room temperature, and poured into ice water. The aimed crystalline product thus formed was separated by filtration, and washed with a small amount of ethanol and ether. Yield: 2.2 g; mp. 151°-155° C.

Example 4 ##STR23##

A mixture of 2 g of N-allyl-ethylenediamine ("J. Am. Chem. Soc.", Vol. 67, pages 1581-1582), 2.7 g of N-nitro-S-methyl-isothiourea and 20 ml of ethanol was stirred at 60° C. for 3 hours. The reaction mixture was allowed to cool to room temperature. The aimed crystalline product thus formed was separated by filtration, and washed with a small amount of ethanol, and dried. Yield: 1.4 g; mp. 86°-90° C.

Example 5 ##STR24##

A solution of 3.6 g of N-2-phenoxyethyl-ethylenediamine and 2.9 g of dimethyl-N-cyano-dithioimino-carbonate in 50 ml of ethanol was slowly heated under stirring, and reflexed until the evolution of methyl mercaptane had ceased. After the completion of the reaction, about 2/3 volume of the ethanol was distilled off, and the residue was cooled, so that the aimed crystalline product was formed. The product was separated by filtration, and then dried. Yield: 3.6 g; mp. 93°-95° C.

Furthermore, various compounds of the formula: ##STR25## can be prepared by the same methods as those shown in Examples 3 to 7. These compounds are shown in Table 1.

                                      TABLE 1                                      __________________________________________________________________________     Compound                                                                             Y    A          Z                               Physical                 __________________________________________________________________________                                                           constant                 1     nitro                                                                               CH.sub.2 CH.sub.2                                                                         cyclopropyl                                              2     nitro                                                                               (CH.sub.2).sub.3                                                                          cyclopentyl                                              3     cyano                                                                               CH.sub.2 CH.sub.2                                                                         cyclohexyl                                               4     nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-methyl-cyclohexyl                                      5     nitro                                                                               CH.sub.2 CH.sub.2                                                                         cyclopropylmethyl                                        6     nitro                                                                               CH.sub.2 CH.sub.2                                                                         2,2-dichloro-3,3-dimethyl-cyclopropylmethyl              7     cyano                                                                               (CH.sub.2).sub.3                                                                          cyclohexylmethyl                                         8     nitro                                                                               CH.sub.2 CH.sub.2                                                                         difluoromethyl                                           9     nitro                                                                               (CH.sub.2).sub.3                                                                          trifluoromethyl                                          10    nitro                                                                                ##STR26## 2-fluoroethyl                                            11    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-chloroethyl                   m.p.                                                                           138-140° C.       12    cyano                                                                               (CH.sub.2).sub.3                                                                          2,2,2-trifluoroethyl                                     13    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2,2,2-trichloroethyl                                     14    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2,2,2-tribromoethyl                                      15    cyano                                                                               CH.sub.2 CH.sub.2                                                                         2,2,3,3-tetrafluoroethyl                                 16    nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-chlorobutyl                                            17    cyano                                                                               CH.sub.2 CH.sub.2                                                                         2-methoxyethyl                                           18    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-isopropoxyethyl                                        19    nitro                                                                               (CH.sub.2).sub.3                                                                          2-(2-methoxyethoxy)ethyl                                 20    nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-chloro-phenoxymethyl                                   21    nitro                                                                                ##STR27## 4-nitro-phenoxymethyl                                    22    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-(2,6-dichlorophenoxy)-ethyl   m.p.                                                                           177-179° C.       23    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-(2,6-dichloro-4-trifluoro-methoxyphenoxy)-ethyl                                                              m.p.                                                                           160-162° C.       24    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-(4-chlorophenoxy)-ethyl       m.p. 95-96°                                                             C.                       25    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-(3-chlorophenoxy)-ethyl       m.p.                                                                           108-110° C.       26    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-(2-chlorophenoxy)-ethyl       m.p.                                                                           153-156° C.       27    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-phenoxyethyl                  m.p. 93-95°                                                             C.                       28    cyano                                                                               (CH.sub.2).sub.3                                                                          2-p-tolyloxyethyl                                        29    cyano                                                                                ##STR28## 2-(2,4-dichloro-phenoxy)-ethyl                           30    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-(3-trifluoromethyl-phenoxy)-ethyl                                                                            m.p.                                                                           125-128° C.       31    nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-(3-trifluoromethyl-phenoxy)-propyl                                                                           m.p. 75-79°                                                             C.                       32    cyano                                                                               CH.sub.2 CH.sub.2                                                                         2-(benzyloxy)-ethyl                                      33    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-(5-chloro-2-pyridyloxy)-ethyl m.p.                                                                           189-191° C.       34    nitro                                                                                CH.sub.2 CH.sub.2                                                                        2-(3,5-dichloro-2-pyridyloxy)-ethyl                                                                            m.p.                                                                           191-192° C.       35    cyano                                                                               (CH.sub.2).sub.3                                                                          ethylthioethyl                                           36    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-ethylthioethyl                                         37    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-ethylsulfinylethyl                                     38    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-ethylsulfonylethyl                                     39    cyano                                                                               (CH.sub.2).sub.3                                                                          2-isopropylthioethyl                                     40    nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-methylthio-propyl             m.p. 93-95°                                                             C.                       41    nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-chloro-phenylthiomethyl                                42    cyano                                                                               CH.sub.2 CH.sub.2                                                                         2-(2-chlorophenylthio)-ethyl                             43    cyano                                                                               CH.sub.2 CH.sub.2                                                                         2-(4-nitro-phenylthio)-ethyl                             44    nitro                                                                               (CH.sub.2).sub.3                                                                          2-(2-chloro-6-pyridylthio)-ethyl                         45    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-(2-thiazolylthio)-ethyl                                46    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-thiocyanato-ethyl                                      47    nitro                                                                               CH.sub.2 CH.sub.2                                                                         thiocyanato-methyl              m.p.                                                                           261-265° C.       48    cyano                                                                               (CH.sub.2).sub.3                                                                          2-dimethylamino-ethyl                                    49    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-Nmethyl-Nbutylamino-ethyl                              50    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-(4-chloro-2-methylanilino)-ethyl                       51    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-(Nmethylanilino)-ethyl                                 52    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-(Nmethyl-N2-chloro-6-pyridylamino)-ethyl               53    nitro                                                                               (CH.sub.2).sub.3                                                                          cyanomethyl                                              54    nitro                                                                                CH.sub.2 CH.sub.2                                                                        1-cyanoethyl                                             55    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-cyanoethyl                    m.p.                                                                           136-139° C.       56    cyano                                                                               CH.sub.2 CH.sub.2                                                                         3-cyanopropyl                                            57    nitro                                                                               CH.sub.2 CH.sub.2                                                                         acetylmethyl                                             58    nitro                                                                               CH.sub.2 CH.sub.2                                                                         3,3-dimethyl-2-butanon-1-yl     m.p.                                                                           158-159° C.       59    cyano                                                                               CH.sub.2 CH.sub.2                                                                         3,3-dimethyl-2-butanon-1-yl     m.p.                                                                           141-145° C.       60    nitro                                                                                ##STR29## benzoylmethyl                                            61    nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-chlorobenzoyl-methyl                                   62    nitro                                                                               CH.sub.2 CH.sub.2                                                                         α-naphthoyl-methyl                                 63    cyano                                                                               (CH.sub.2).sub.3                                                                          trifluoroacetyl-methyl                                   64    cyano                                                                               CH.sub.2 CH.sub.2                                                                         2-acetylethyl                                            65    nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-pyridylcarbonyl-methyl        m.p.                                                                           192-194° C.       66    nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-pyridylcarbonyl-methyl        m.p.                                                                           176-177° C.       67    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-pyridylcarbonyl-methyl        m.p.                                                                           169-173° C.       68    cyano                                                                               (CH.sub.2).sub.3                                                                          ethoxycarbonyl-methyl                                    69    nitro                                                                               CH.sub.2 CH.sub.2                                                                         1-ethoxycarbonyl-ethyl          m.p. 66-69°                                                             C.                       70    nitro                                                                               CH.sub.2 CH.sub.2                                                                         phenoxycarbonylmethyl                                    71    cyano                                                                               (CH.sub.2).sub.3                                                                          3-methylphenoxy-carbonylmethyl                           72    nitro                                                                                ##STR30## benzyloxycarbonyl-methyl                                 73    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-methoxycarbonyl-ethyl                                  74    nitro                                                                               CH.sub.2 CH.sub.2                                                                         carbamoylmethyl                                          75    cyano                                                                               (CH.sub.2).sub.3                                                                          isopropylaminocarbonyl-methyl                            76    nitro                                                                               CH.sub.2 CH.sub.2                                                                         dimethylaminocarbonyl-methyl                             77    nitro                                                                               (CH.sub.2).sub.3                                                                          1-diethylamino-carbonyl-ethyl                            78    nitro                                                                               CH.sub.2 CH.sub.2                                                                         anilinocarbonyl-methyl                                   79    nitro                                                                               CH.sub.2 CH.sub.2                                                                         Nmethylanilocarbonyl-methyl                              80    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-diethylamino-carbonyl-ethyl                            81    nitro                                                                               CH.sub.2 CH.sub.2                                                                         hydroxymethyl                                            82    nitro                                                                               (CH.sub.2).sub.3                                                                          hydroxymethyl                                            83    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-hydroxy-ethyl                 m.p.                                                                           128-130° C.       84    cyano                                                                               CH.sub.2 CH.sub.2                                                                         3-hydroxy-propyl                                         85    nitro                                                                               CH.sub.2 CH.sub.2                                                                         1,3-dihydroxy-propyl                                     86    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-acetyloxy-ethyl                                        87    cyano                                                                               CH.sub.2 CH.sub.2                                                                         2-trifluoro-acetyloxy-ethyl                              88    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-benzoyloxy-ethyl                                       89    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-methylsulfonyloxy-ethyl                                90    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-tosyloxy-ethyl                                         91    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-dimethylamino-carbonyloxyethyl                         92    nitro                                                                               CH.sub. 2 CH.sub.2                                                                        2,2,2-trichloro-1-hydroxyethyl                           93    nitro                                                                               CH.sub.2 CH.sub.2                                                                         α-hydroxy-4-chloro-benzyl                          94    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-(O,Odiethyl-thiophosphono-thio)-ethyl                  95    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-(Oethyl-Spropylthiophosphono-oxy)-ethyl                96    nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-(O,Odimethylphosphono)-ethyl                           97    nitro                                                                               CH.sub.2 CH.sub.2                                                                         trimethylsilyl-methyl                                    98    cyano                                                                               CH.sub.2 CH.sub.2                                                                         2-trimethylsilyl-ethyl                                   99    cyano                                                                               CH.sub.2 CH.sub.2                                                                         trimethylsilylmethyl                                     100   nitro                                                                               (CH.sub.2).sub.3                                                                          7-quinolyl-methyl                                        101   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-chloro-isoquinolin-4-yl-methyl                                                                               m.p.                                                                           220-222° C.       102   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-methylthio-1,3-benzothiazol-5-yl-methyl                103   cyano                                                                               CH.sub.2 CH.sub.2                                                                         6-quinoxalinyl                                           104   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-chloro-1,3-benzothiazol-6-yl-methyl                                                                          m.p.                                                                           218-221° C.       105   cyano                                                                                ##STR31## phenyl                                                   106   cyano                                                                               CH.sub.2 CH.sub.2                                                                         2,4-dichloro-phenyl                                      107   nitro                                                                               (CH.sub.2).sub.3                                                                          4-nitrophenyl                                            108   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-(4-trifluoromethyl-phenoxy)-phenyl                     109   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3,5-dichloro-2-pyridyl          m.p.                                                                           151-155° C.       110   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-thiazolyl                     m.p.                                                                           159-162° C.       111   cyano                                                                               (CH.sub.2).sub.3                                                                          1,3,4-thiadiazol-2-yl                                    112   nitro                                                                               CH.sub.2 CH.sub.2                                                                         5-methyl-2-pyrimidinyl                                   113   cyano                                                                               (CH.sub.2).sub.3                                                                          1,3-benzothiazol-2-yl                                    114   nitro                                                                               CH.sub.2 CH.sub.2                                                                         1,3-benzoxazol-2-yl             m.p. >250°                                                              C.                       115   nitro                                                                               CH.sub.2 CH.sub.2                                                                         6-fluoro-2-quinolyl                                      116   nitro                                                                               CH.sub.2 CH.sub.2                                                                         6-chloro-2-quinoxalinyl                                  117   cyano                                                                               CH.sub.2 CH.sub.2                                                                         4-pyridyl                                                118   nitro                                                                               CH.sub.2 CH.sub.2                                                                         5-trifluoromethyl-2-pyridyl     m.p.                                                                           239-241° C.       119   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4,5-dichloro-2-thiazolyl                                 120   nitro                                                                               CH.sub.2 CH.sub.2                                                                         allyl                           m.p. 86-90°                                                             C.                       121   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-pentenyl                                               122   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-chloroallyl                   m.p.                                                                           110-113° C.       123   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-chloro-2-butenyl              m.p.                                                                           224-227° C.       124   cyano                                                                                ##STR32## 2,3,3-trichloro-allyl                                    125   nitro                                                                               (CH.sub.2).sub.3                                                                          propargyl                                                126   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-iodo-propargyl                                         127   nitro                                                                               CH.sub.2 CH.sub.2                                                                         methoxy                                                  128   nitro                                                                               CH.sub.2 CH.sub.2                                                                         ethoxy                                                   129   cyano                                                                               CH.sub. 2 CH.sub.2                                                                        phenoxy                                                  130   nitro                                                                               (CH.sub.2).sub.3                                                                          benzyloxy                                                131   nitro                                                                               CH.sub.2 CH.sub.2                                                                         allyloxy                                                 132   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-pyridylmethyloxy                                       133   nitro                                                                               (CH.sub.2).sub.3                                                                          methylthio                                               134   nitro                                                                               CH.sub.2 CH.sub.2                                                                         isopropylthio                                            135   nitro                                                                               CH.sub.2 CH.sub.2                                                                         trichloromethylthio                                      136   nitro                                                                               CH.sub.2 CH.sub.2                                                                         chloro-difluoromethyl-thio                               137   cyano                                                                               CH.sub.2 CH.sub.2                                                                         4-chloro-phenylthio                                      138   nitro                                                                               CH.sub.2 CH.sub.2                                                                         p-tolylthio                                              139   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-chloro-benzylthio                                      140   nitro                                                                               CH.sub.2 CH.sub.2                                                                         dimethylamino                                            141   nitro                                                                               (CH.sub.2).sub.3                                                                          diethylamino                                             142   cyano                                                                               CH.sub.2 CH.sub.2                                                                         ethyl-carbonyl                  m.p.                                                                           208-210° C.       143   cyano                                                                                ##STR33## isopropyl-carbonyl                                       144   nitro                                                                               CH.sub.2 CH.sub.2                                                                         n-propylcarbonyl                m.p.                                                                           126-130° C.       145   nitro                                                                               CH.sub.2 CH.sub.2                                                                         n-butylcarbonyl                                          146   nitro                                                                               CH.sub.2 CH.sub.2                                                                         n-octylcarbonyl                                          147   cyano                                                                               (CH.sub.2).sub.3                                                                          cyclopropylcarbonyl                                      148   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2,2-dichloro-3,3-dimethyl-cyclopropyl-carbonyl           149   nitro                                                                               CH.sub.2 CH.sub.2                                                                         cyclohexyl-carbonyl                                      150   nitro                                                                               (CH.sub.2).sub.3                                                                          4-methyl-cyclohexyl-carbonyl                             151   nitro                                                                               CH.sub.2 CH.sub.2                                                                         bromoacetyl                     mp. 136-140°                                                            C.                                                                             (decomp.)                152   cyano                                                                               CH.sub.2 CH.sub.2                                                                         trifluoro-acetyl                                         153   nitro                                                                               (CH.sub.2).sub.3                                                                          trichloro-acetyl                                         154   nitro                                                                               CH.sub.2 CH.sub.2                                                                         dichloroacetyl                                           155   nitro                                                                               CH.sub.2 CH.sub.2                                                                         1,1-dichloroethyl-carbonyl                               156   nitro                                                                               CH.sub.2 CH.sub.2                                                                         methoxyacetyl                                            157   nitro                                                                               CH.sub.2 CH.sub.2                                                                         1-(4-chlorophenoxy)-ethyl-carbonyl                       158   nitro                                                                               CH.sub.2 CH.sub.2                                                                         methylthioacetyl                                         159   nitro                                                                               CH.sub.2 CH.sub.2                                                                         acetyloxy-acetyl                                         160   nitro                                                                               (CH.sub.2).sub.3                                                                          acryloyl                                                 161   cyano                                                                               (CH.sub.2).sub.3                                                                          1-propenyl-carbonyl                                      162   cyano                                                                               CH.sub.2 CH.sub.2                                                                         trichloro-acryloyl                                       163   nitro                                                                               CH.sub.2 CH.sub.2                                                                         propargyl-carbonyl                                       164   nitro                                                                               CH.sub.2 CH.sub.2                                                                         benzylcarbonyl                                           165   nitro                                                                               CH.sub.2 CH.sub.2                                                                         cyanoacetyl                                              166   nitro                                                                               CH.sub.2 CH.sub.2                                                                         1-cyano-ethylcarbonyl                                    167   nitro                                                                               CH.sub.2 CH.sub.2                                                                         acetyl-acetyl                                            168   cyano                                                                               CH.sub.2 CH.sub.2                                                                         5-quinolyl-carbonyl                                      169   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3,7-dichloro-5-quinolylcarbonyl                          170   nitro                                                                               CH.sub.2 CH.sub. 2                                                                        6-quinoxalyl-carbonyl                                    171   nitro                                                                                ##STR34## cyclopentyloxy-carbonyl                                  172   cyano                                                                               (CH.sub.2).sub.3                                                                          2-methyl-cyclohexyloxy-carbonyl                          173   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-methoxy-ethoxy-carbonyl                                174   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-(3,4-dichloro-phenoxy)-ethoxy-carbonyl                 175   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-diethylamino-ethoxy-carbonyl                           176   nitro                                                                               (CH.sub.2).sub.2                                                                          2-ethylthio-ethoxy-carbonyl                              177   cyano                                                                               CH.sub.2 CH.sub.2                                                                         2-chloro-ethoxy-carbonyl                                 178   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2,2,2-trifluoro-ethoxy-carbonyl                          179   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-bromo-propoxy-carbonyl                                 180   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2,2,3,3-tetrafluoro-propoxy-carbonyl                     181   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-hydroxy-ethoxycarbonyl                                 182   nitro                                                                               CH.sub.2 CH.sub.2                                                                         allyloxy-carbonyl                                        183   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-chloro-allyloxy-carbonyl                               184   nitro                                                                               (CH.sub.2).sub.3                                                                          2,3,3-trichloro-allyloxy-carbonyl                        185   nitro                                                                               CH.sub.2 CH.sub.2                                                                         propargyloxy-carbonyl                                    186   cyano                                                                               CH.sub.2 CH.sub.2                                                                         3-iodo-propargyloxy-carbonyl                             187   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-chloro-phenoxy-carbonyl                                188   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-nitro-m-tolyloxy-carbonyl                              189   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-chloro-o-tolyloxy-carbonyl                             190   nitro                                                                               (CH.sub.2).sub.3                                                                          4-trifluoromethyl-phenoxy-carbonyl                       191   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-dimethylamino-phenoxy-carbonyl                         192   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-bromo-2-chloro-phenoxy-carbonyl                        193   cyano                                                                               CH.sub.2 CH.sub.2                                                                         2,5-dichloro-4-iodo-phenoxy-carbonyl                     194   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-methylthio-m-tolyloxy-carbonyl                         195   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-methylsulfinyl-phenoxy-carbonyl                        196   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-cyanophenoxy-carbonyl                                  197   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-isopropoxycarbonyl-phenoxy-carbonyl                    198   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-sec-butyl-phenoyx-carbonyl                             199   nitro                                                                               (CH.sub.2).sub.3                                                                          2-isopropoxy-phenoxy-carbonyl                            200   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy-carbonyl      201   cyano                                                                               CH.sub.2 CH.sub.2                                                                         ethylthio-carbonyl                                       202   cyano                                                                               CH.sub.2 CH.sub.2                                                                         phenylthio-carbonyl                                      203   nitro                                                                               CH.sub.2 CH.sub.2                                                                         benzyloxy-carbonyl              m.p.                                                                           179-182° C.       204   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2,4-dichloro-benzyloxy-carbonyl                          205   nitro                                                                                ##STR35## 3-trifluoromethyl-benzyloxy-carbonyl                     206   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-methoxybenzyloxy-carbonyl                              207   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-phenoxybenzyloxy-carbonyl                              208   nitro                                                                               CH.sub.2 CH.sub.2                                                                         α-methylbenzyloxy-carbonyl                         209   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-pyridyloxy-carbonyl                                    210   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3,5,6-trichloro-2-pyridyloxy-carbonyl                    211   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-thienyloxy-carbonyl                                    212   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-methyl-5-pyrazolyloxy-carbonyl                         213   nitro                                                                               CH.sub.2 CH.sub.2                                                                         5-phenyl-3-iso-oxazolyloxy-carbonyl                      214   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-methyl-1-isopropyl-5-pyrazolyloxy-carbonyl             215   nitro                                                                               CH.sub.2 CH.sub.2                                                                         5-chloro-1-isopropyl-1,2,4-traizol-3-yl-oxy-carbonyl                           5                                                        216   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-pyrazyloxy-carbonyl                                    217   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-isopropyl-6-methyl-4-pyrimidinyloxy-carbonyl           218   nitro                                                                               CH.sub.2 CH.sub.2                                                                         1H6-oxo-3-pyridazinyloxy-carbonyl                        219   nitro                                                                               CH.sub.2 CH.sub.2                                                                         1-phenyl-6-oxo-3-pyridazinyloxy-carbonyl                 220   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-quinoxalinyloxy-carbonyl                               221   nitro                                                                               CH.sub.2 CH.sub.2                                                                         1-benzothiophen-4-yl-oxy-carbonyl                        222   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2,2-dimethyl-dihydro-benzofuran-7-yl-oxy-carbonyl        223   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-chloro-4-methyol-2-oxo-2H1-benzopyran-7-yl-oxy-car                           bonyl                                                    224   cyano                                                                               CH.sub.2 CH.sub.2                                                                         carbamoyl                                                225   nitro                                                                               CH.sub.2 CH.sub.2                                                                         ethylamino-carbonyl             m.p.                                                                           145-148° C.       226   nitro                                                                               CH.sub.2 CH.sub.2                                                                         isopropylamino-carbonyl         m.p.                                                                           148-150° C.       227   nitro                                                                               (CH.sub.2).sub.3                                                                          cyclohexylamino-carbonyl                                 228   cyano                                                                               CH.sub.2 CH.sub.2                                                                         anilino-carbonyl                                         229   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-chloro-4-fluoro-anilino-carbonyl                       230   nitro                                                                                ##STR36## 2,6-diethylanilino-carbonyl                              231   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2,4-dichloro-5-isopropoxy-anilino-carbonyl               232   nitro                                                                                CH.sub.2 CH.sub.2                                                                        dimethylamino-carbonyl          m.p.                                                                           147-148° C.       233   nitro                                                                               (CH.sub.2).sub.3                                                                          diethylamino-carbonyl                                    234   nitro                                                                               CH.sub.2 CH.sub.2                                                                         diisobutylamino-carbonyl                                 235   nitro                                                                               (CH.sub.2).sub.3                                                                          pyrrolidino-carbonyl                                     236   cyano                                                                               CH.sub.2 CH.sub.2                                                                         2-piperidino-carbonyl                                    237   cyano                                                                               CH.sub.2 CH.sub.2                                                                         2,6-dimethyl-morpholino-carbonyl                         238   nitro                                                                               CH.sub.2 CH.sub.2                                                                         Nmethyl-m-toluidino-carbonyl                             239   nitro                                                                               CH.sub.2 CH.sub.2                                                                         Nisopropylanilino-carbonyl                               240   nitro                                                                               CH.sub.2 CH.sub.2                                                                         Nmethyl-2,6-diethyl-anilino-carbonyl                     241   nitro                                                                               CH.sub.2 CH.sub.2                                                                         N,Ndiphenylamino-carbonyl                                242   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-pyridylamino-carbonyl                                  243   nitro                                                                               CH.sub.2 CH.sub.2                                                                         Nmethyl-2-methoxy-6-pyridyl-amino-carbonyl               244   nitro                                                                               CH.sub.2 CH.sub.2                                                                         Nmethyl-furylamino-carbonyl                              245   nitro                                                                               CH.sub.2 CH.sub.2                                                                         Nmethyl-iso-oxazolylamino-carbonyl                       246   nitro                                                                               CH.sub.2 CH.sub.2                                                                         5-tert-butyl-3-iso-oxazolylamino-carbonyl                247   nitro                                                                               CH.sub.2 CH.sub.2                                                                         5-chloro-4-methyl-2-thiazolylamino-carbonyl              248   nitro                                                                               CH.sub.2 CH.sub.2                                                                         Nmethyl-2-trifluoromethyl-1,3,4-thiadiazol-5-yl-amin                           o-carbonyl                                               249   nitro                                                                               CH.sub.2 CH.sub.2                                                                         Nmethyl-2-ethylsulfonyl-1,3,4-thiadiazol-5-yl-amino-                           carbonyl                                                 250   nitro                                                                               (CH.sub.2).sub.3                                                                          3-pyridylamino-carbonyl                                  251   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-benzimidazolyl-amino-carbonyl                          252   nitro                                                                               CH.sub.2 CH.sub.2                                                                         N methyl-benzylamino-carbonyl                            253   nitro                                                                               (CH.sub.2).sub.3                                                                          α,α-dimethyl-benzylamino-carbonyl            254   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-picolylamino-carbonyl                                  255   nitro                                                                               CH.sub.2 CH.sub.2                                                                         Nmethyl-2-furfurylamino-carbonyl                         256   nitro                                                                               CH.sub.2 CH.sub.2                                                                         Nmethyl-2-tetrahydrofurfurylamino-carbonyl               257   nitro                                                                               CH.sub.2 CH.sub.2                                                                         Nmethyl-perhydrooxazin-2-yl-methyl-amino-carbonyl        258   nitro                                                                               CH.sub.2 CH.sub.2                                                                         allylamino-carbonyl                                      259   nitro                                                                               CH.sub.2 CH.sub.2                                                                         propargylamino-carbonyl                                  260   cyano                                                                               CH.sub.2 CH.sub.2                                                                         N,Ndiallylamino-carbonyl                                 261   nitro                                                                               CH.sub.2 CH.sub.2                                                                         ethoxyalyl                                               262   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-chloro-phenoxalyl                                      263   nitro                                                                               CH.sub.2 CH.sub.2                                                                         benzyl-oxalyl                                            264   nitro                                                                               CH.sub.2 CH.sub.2                                                                         methyl-sulfonyl                                          265   nitro                                                                               (CH.sub.2).sub.3                                                                          chloromethyl-sulfonyl                                    266   cyano                                                                               CH.sub.2 CH.sub.2                                                                         trifluoromethyl-sulfonyl                                 267   nitro                                                                               CH.sub.2 CH.sub.2                                                                         n-butyl-sulfonyl                                         268   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-chloroethyl-sulfonyl                                   269   nitro                                                                               (CH.sub.2).sub.3                                                                          phenylsulfonyl                                           270   nitro                                                                               CH.sub.2 CH.sub.2                                                                         tosyl                                                    271   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-chlorophenyl-sulfonyl                                  272   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-nitrophenyl-sulfonyl                                   273   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-methyl-5-nitrophenyl-sulfonyl m.p.                                                                           193-197°                                                                C.                       274   cyano                                                                               CH.sub.2 CH.sub.2                                                                         methoxy-sulfonyl                                         275   nitro                                                                               CH.sub.2 CH.sub.2                                                                         cyclohexyloxy-carbonyl                                   276   nitro                                                                                ##STR37## phenoxy-sulfonyl                                         277   nitro                                                                               CH.sub.2 CH.sub.2                                                                         methylamino-sulfonyl                                     278   nitro                                                                               CH.sub.2 CH.sub.2                                                                         isopropylamino-sulfonyl                                  279   nitro                                                                               CH.sub.2 CH.sub.2                                                                         diethylamino-sulfonyl                                    280   nitro                                                                               CH.sub.2 CH.sub.2                                                                         anilino-sulfonyl                                         281   nitro                                                                               CH.sub.2 CH.sub.2                                                                         Nmethylanilino-sulfonyl                                  282   nitro                                                                               CH.sub.2 CH.sub.2                                                                         O,Odimethyl-phosphono                                    283   nitro                                                                               CH.sub.2 CH.sub.2                                                                         Oethyl-Oisopropyl-phosphono                              284   nitro                                                                               CH.sub.2 CH.sub.2                                                                         Oethyl-Spropyl-thio-phosphono                            285   nitro                                                                               CH.sub.2 CH.sub.2                                                                         O,Odiethylthio-phosphono                                 286   nitro                                                                               CH.sub.2 CH.sub.2                                                                         Oethyl-O2,4-dichlorophenylthio-phosphono                 287   nitro                                                                               CH.sub.2 CH.sub.2                                                                         Oethyl-Nisopropylamido-thio-phosphono                    288   nitro                                                                               CH.sub.2 CH.sub.2                                                                          ##STR38##                                               289   nitro                                                                               CH.sub.2 CH.sub.2                                                                          ##STR39##                                               290   nitro                                                                               CH.sub.2 CH.sub.2                                                                          ##STR40##                                               291   nitro                                                                               CH.sub.2 CH.sub.2                                                                          ##STR41##                                               292   nitro                                                                               CH.sub.2 CH.sub.2                                                                          ##STR42##                                               293   nitro                                                                               CH.sub.2 CH.sub.2                                                                          ##STR43##                                               294   nitro                                                                               CH.sub.2 CH.sub.2                                                                          ##STR44##                                               295   nitro                                                                               CH.sub.2 CH.sub.2                                                                          ##STR45##                                               296   nitro                                                                               CH.sub.2 CH.sub.2                                                                          ##STR46##                                               297   nitro                                                                               CH.sub.2 CH.sub.2                                                                         n-butyl                         mp. 65-68°                                                              C.                       298   nitro                                                                               CH.sub.2 CH.sub.2                                                                         tert-butyl                                               299   cyano                                                                               CH.sub.2 CH.sub.2                                                                         n-octyl                                                  300   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-methyl-benzyl                                          301   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-chloro-benzyl                                          302   cyano                                                                               CH.sub.2 CH.sub.2                                                                         2-bromo-benzyl                                           303   nitro                                                                               (CH.sub.2).sub.3                                                                          2,4-dichloro-benzyl                                      304   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-nitro-benzyl                                           305   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-methoxy-benzyl                                         306   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-trifluoromethyl-benzyl                                 307   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3,4-methylenedioxy-benzyl                                308   nitro                                                                               CH.sub.2 CH.sub.2                                                                         α-methylbenzyl                                     309   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-bromobenzyl                                            310   cyano                                                                               CH.sub.2 CH.sub.2                                                                         2-furfuryl                                               311   nitro                                                                               CH.sub.2 CH.sub.2                                                                         5-methyl-2-furfuryl                                      312   nitro                                                                                ##STR47## 2-thienyl                                                313   nitro                                                                               CH.sub.2 CH.sub.2                                                                         5-bromo-2-thienyl                                        314   nitro                                                                               CH.sub.2 CH.sub.2                                                                         1-methyl-2-pyrrolyl-methyl                               315   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-phenyl-5-iso-oxazolyl-methyl                           316   nitro                                                                               CH.sub.2 CH.sub.2                                                                         5-imidazolyl-methyl                                      317   nitro                                                                               CH.sub.2 CH.sub.2                                                                         5-isothiazolyl-methyl                                    318   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-methyl-thiazolyl-methyl                                319   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-trifluoromethyl-1,3,4-oxadiazol-5-yl-methyl            320   nitro                                                                               CH.sub.2 CH.sub.2                                                                         1,3,4-thiadiazol-2-yl-methyl                             321   nitro                                                                               CH.sub.2 CH.sub.2                                                                         1,2,3,4-tetrazol-5-yl-methyl                             322   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-pyrimiinyl-methyl                                      323   nitro                                                                               CH.sub.2 CH.sub.2                                                                         6-chloro-4-pyrazinyl-methyl                              324   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4,6-dichloro-1,3,5-triazin-2-yl-methyl                   325   cyano                                                                               CH.sub.2 CH.sub.2                                                                         2-(2-furyl)-ethyl                                        326   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-(2-chloro-6-pyridyl)-ethyl    mp. 170-173°                                                            C.                       327   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-(2-chloro-5-pyridyl)-propyl   mp.                                                                            116-118.5°                                                              C.                       328   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-tetrahydro-furfuryl                                    329   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-tetrahydrothienyl-methyl                               330   nitro                                                                               CH.sub.2 CH.sub.2                                                                         1-methyl-2-pyrrolidinyl-methyl                           331   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4,5-dihydro-iso-oxazol-5-yl-methyl                       332   nitro                                                                                CH.sub.2 CH.sub.2                                                                        3-methyl-5-tetrahydro-thiazolyl-methyl                   333   nitro                                                                               CH.sub.2 CH.sub.2                                                                         5-oxo-2-tetrahydro-furfuryl                              334   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-methyl-2-oxo-5-tetrahydro-thiazolyl-methyl             335   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-oxo-1,3-dioxolan-4-yl-methyl                           336   nitro                                                                               CH.sub.2 CH.sub.2                                                                         1,3-dioxolan-2-yl-methyl                                 337   nitro                                                                               CH.sub.2 CH.sub.2                                                                         1,3-oxathiolan-2-yl-methyl                               338   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-tetrahydro-pyranyl-methyl                              339   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-tetrahydro-thio-pyranyl-methyl                         340   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-oxo-1,3-oxathian-5-yl-methyl                           341   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-methyl-1,4-oxazin-2-yl-methyl                          342   nitro                                                                               CH.sub.2 CH.sub.2                                                                         1-ethyl-4-piperazinyl-methyl                             343   nitro                                                                               CH.sub.2 CH.sub.2                                                                         1-methyl-2-oxo-4-piperazinyl                             344   nitro                                                                               (CH.sub.2).sub.3                                                                          methoxy-carbonyl                                         345   nitro                                                                               CH.sub.2 CH.sub.2                                                                         isopropoxy-carbonyl                                      346   nitro                                                                               (CH.sub.2).sub.3                                                                          hexyloxy-carbonyl                                        347   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2,4-dichloro-benzoyl            mp. 184-186°                                                            C.                       348   cyano                                                                               CH.sub.2 CH.sub.2                                                                         3,5-dichloro-benzoyl            mp. 231-232°                                                            C.                       349   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-methyl-benzoyl                                         350   cyano                                                                               CH.sub.2 CH.sub.2                                                                         4-trifluoromethyl-benzoyl                                351   nitro                                                                               (CH.sub.2).sub.3                                                                          3,4-dimethoxy-benzoyl                                    352   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-nitro-benzoyl                                          353   nitro                                                                               CH.sub. 2 CH.sub.2                                                                        2-acetylamino-benzoyl                                    354   nitro                                                                               CH.sub.2 CH.sub.2                                                                         α-naphthoyl                                        355   cyano                                                                               CH.sub.2 CH.sub.2                                                                         2,5-dichloro-benzoyl                                     356   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-ethoxy-methoxy-benzoyl                                 357   nitro                                                                               (CH.sub.2).sub.3                                                                          2-pyridyl-carbonyl                                       358   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-chloro-5-pyridyl-carbonyl                              359   cyano                                                                               (CH.sub.2).sub.3                                                                          4-pyridyl-carbonyl                                       360   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2,6-dichloro-4-pyridyl-carbonyl                          361   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-furyl-carbonyl                mp. 160-162°                                                            C.                       362   nitro                                                                               CH.sub.2 CH.sub.2                                                                         5-nitro-2-furyl-carbonyl                                 363   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2,5-dimethyl-3-furyl-carbonyl                            364   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-thienyl-carbonyl                                       365   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3,5-dichloro-2-thienyl-carbonyl                          366   nitro                                                                               CH.sub.2 CH.sub.2                                                                         1-methyl-4-pyrazolyl-carbonyl                            367   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-trifluoromethyl-5-iso-oxazolyl-carbonyl                368   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-oxazolyl-carbonyl                                      369   cyano                                                                               CH.sub.2 CH.sub.2                                                                         2-thiazolyl-carbonyl                                     370   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-chloro-5-thiazolyl-carbonyl                            371   nitro                                                                               (CH.sub.2).sub.3                                                                          2,4-dichloro-5-thiazolyl-carbonyl                        372   nitro                                                                               CH.sub.2 CH.sub.2                                                                         5-isothiazolyl-carbonyl                                  373   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-tert-butyl-1,3,4-oxadiazol-5-yl-carbonyl               374   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-phenyl-1,3,4-thiadiazol-5-yl-carbonyl                  375   nitro                                                                               CH.sub.2 CH.sub.2                                                                         1,2,3-thiadiazol-5-yl-carbonyl                           376   nitro                                                                               CH.sub.2 CH.sub.2                                                                         5-tert-butyl-2-pyrimidinyl-carbonyl                      377   nitro                                                                               CH.sub.2 CH.sub.2                                                                         5-methyl-2-pyrazinyl-carbonyl                            378   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-pyridazinyl-carbonyl                                   379   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4,6-dichloro-1,3,5-triazin-2-yl-carbonyl                 380   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4,6-dimethylthio-1,3,5-triazin-2-yl-carbonyl             381   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-tetrahydro-furyl-carbonyl                              382   cyano                                                                               CH.sub.2 CH.sub.2                                                                         2-tetrahydro-thienyl-carbonyl                            383   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-methyl-3-oxo-5-tetrahydro-iso-oxazolyl-carbonyl        384   nitro                                                                               (CH.sub.2).sub.3                                                                          1-methyl-3-pyrrolidinyl-carbonyl                         385   cyano                                                                               CH.sub.2 CH.sub.2                                                                         2-oxo-5-tetrahydro-thiazolyl-carbonyl                    386   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-methyl-5-tetrahydro-thiazolyl-carbonyl                 387   nitro                                                                               CH.sub.2 CH.sub.2                                                                         1-phenyl-4-piperazinyl-carbonyl                          388   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-methyl-1,4-oxazin-2-yl-carbonyl                        389   nitro                                                                               CH.sub.2 CH.sub.2                                                                         phenethyl                                                390   nitro                                                                               CH.sub.2 CH.sub.2                                                                         dimethylamino-thio-carbonyl                              391   cyano                                                                               (CH.sub.2).sub.3                                                                          1-piperidino-thio-carbonyl                               392   nitro                                                                               CH.sub.2 CH.sub.2                                                                         Nmethyl-N(2-methoxypyridin-6-yl)-amino-thio-carbonyl     393   nitro                                                                               (CH.sub.2).sub.3                                                                          3-chloroallyl                   n.sub.D 1.5985           394   nitro                                                                               CH.sub.2 CH.sub.2                                                                         Oethyl-Ssec-butyl-thio-phosphono                                                                               n.sub.D 1.5550           395   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-pyrimidinyl                   mp. 185-188°                                                            C.                       396   nitro                                                                               CH.sub.2 CH.sub.2                                                                         pyrazinyl                       mp. 179-182°                                                            C.                       397   nitro                                                                               CH.sub.2 CH.sub.2                                                                         6-chloro-3-pyridazinyl          mp. 242-246°                                                            C.                                                                             (decomp.)                398   nitro                                                                               CH.sub.2 CH.sub.2                                                                         6-chloro-4-pyrimidinyl          mp. 250-251°                                                            C.                       399   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4,6-dimethoxy-1,3,5-triazin-2-yl                                                                               mp. 210-212°                                                            C.                                                                             (decomp.)                400   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-(2-pyridyl)-ethyl             mp. 105-109°                                                            C.                       401   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2,2-dimethoxy-ethyl                                      402   cyano                                                                               CH.sub.2 CH.sub.2                                                                         2,2-dimethoxy-ethyl                                      403   nitro                                                                               CH.sub.2 CH.sub.2                                                                         cyano                           mp. 176-180°                                                            C.                                                                             (decomp.)                404   cyano                                                                               CH.sub.2 CH.sub.2                                                                         cyano                           mp. >300°                                                               C.                       405   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-chloro-2-cyanoethyl           n.sub.D.sup.20                                                                 1.5776                   406   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-chloro-2-cyanovinyl           mp. 128-131°                                                            C.                       407   nitro                                                                               CH.sub.2 Ch.sub.2                                                                         3-cyanobenzyl                   mp. 169-172°                                                            C.                       408   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-cyanobenzyl                   mp. 203-205°                                                            C.                       409   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-cyanobenzyl                   mp. 148-150°                                                            C.                       410   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-cyano-4-fluoro-benzyl         mp. 159-161°                                                            C.                       411   cyano                                                                               CH.sub.2 CH.sub.2                                                                         3-cyanobenzyl                   mp. 146-150°                                                            C.                       412   nitro                                                                               (CH.sub.2).sub.3                                                                          3-cyanobenzyl                   mp. 140-142°                                                            C.                       413   nitro                                                                               CH.sub.2 CH.sub.2                                                                         phenyl                          mp. 150-153°                                                            C.                       414   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-(2,2,2-trifluoro-ethylthio)benzyl                                                                            mp. 85-88°                                                              C.                       415   nitro                                                                               CH.sub.2 CH.sub.2                                                                         3-(2,2,2-trifluoro-ethoxy)benzyl                                                                               mp. 95-99°                                                              C.                       416   nitro                                                                               CH.sub.2 CH.sub.2                                                                         6-chloronicotinoylmethyl        mp. 221-225°                                                            C.                       417   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-(1,1,2,3,3,3-hexafluoro propoxy)benzyl                                                                       n.sub.D.sup.40                                                                 1.5010                   418   nitro                                                                               CH.sub.2 CH.sub.2                                                                         propargyl                       mp. 156-160°                                                            C.                       419   nitro                                                                               Ch.sub.2 CH.sub.2                                                                         n-butylaminocarbonyl            mp. 103-107°                                                            C.                       420   nitro                                                                               CH.sub.2 CH.sub.2                                                                         anilinocarbonyl                 mp. 192-195°                                                            C.                       421   nitro                                                                               CH.sub.2 CH.sub.2                                                                         2-methoxyanilinocarbonyl        mp. 207-211°                                                            C.                       422   nitro                                                                               CH.sub.2 CH.sub.2                                                                         4-chloro-3-cyanobenzyl          mp. 179-181°                                                            C.                       __________________________________________________________________________

Referential example 1 ##STR48##

3.2 g of 1-[2-(3,5-dichloropyridyl-2-yl-oxy)ethyl]-2-nitroiminoimidazolidine were dissolved in 20 ml of dimethyl-formamide. To the resulting solution was added 0.4 g of 60% oil dispersed sodium hydride at room temperature. The reaction mixture thus obtained was stirred until the evolution of hydrogen had ceased. Next, 1.7 g of 2-chloro-5-chloromethylthiazole were added at room temperature, and the reaction mixture was stirred at room temperature for 1 hour, and then stirred at 40° C. for 30 minutes. After the completion of the reaction, the reaction mixture was poured into ice water, and extracted with dichloromethane. The extractant was treated so as to concentrate the dichloromethane. An amount of ether was added to the residue, so that the aimed product was deposited as crystals. The crystalline product was separated by filtration, washed in water and then dried. Yield: 2.7 g; mp. 77° to 80° C.

Referential example 2 ##STR49##

A mixture of 2.1 g of 1-(3,3-dimethyl-2-butanon-1-yl)-2-cyanoiminoimidazolidine, 1.6 g of 2-chloro-5-chloromethylpyridine, 1.4 g of anhydrous potassium carbonate and 30 ml of acetonitrile was refluxed under stirring for 8 hours. After the completion of the reaction, the acetonitrile was distilled off under a reduced pressure. The residue was admixed with dichloromethane and washed in water. After the dichloromethane had been concentrated, the reaction mixture was worked up by employing a silica gel column (wherein chloroform:ethanol=9:1), so that 0.9 g of the aimed product was obtained as a colorless viscous material. n_(D) ²⁰ =1.5446

By the same method as Examples 1 and 2 various compounds of the formula: ##STR50## can be obtained, as shown in Table 2. In Table 2, the mark " " represents the bond of the nitrogen atom in the radical A connected to the bond of ##STR51##

    TABLE 2       Compound W R Y A Z Physical constant        E-1 4-pyridyl H cyano CH.sub.2 CH.sub.2 methyl  E-2 2-chloro-5-pyridyl      H nitro CH.sub.2 CH.sub.2 methyl mp. 107.5-108.5° C.  E-3      2-chloro-5-pyridyl H nitro       methyl  E-4 2-chloro-5-pyridyl H cyano CH.sub.2 CH.sub.2 methyl mp.      101-103° C. E-5 5-thiazolyl H cyano (CH.sub.2).sub.3 methyl E-6      5-chloro-2-pyridyl H nitro CH.sub.2 CH.sub.2 methyl       E-7 1-methyl-4-imidazolyl H nitro       ##STR52##       methyl  E-8 2-methyl-4-pyrazinyl H nitro CH.sub.2 CH.sub.2 methyl E-9      2-methyl-5-oxazolyl H nitro CH.sub.2       CH.sub.2 ethyl E-10 2-chloro-1,3,4-thiadiazol-5-yl H nitro CH.sub.2      CH.sub.2 ethyl E-11 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2      isopropyl mp. 138-142° C. E-12 2-methyl-5-pyrimidinyl H nitro      CH.sub.2 CH.sub.2 isopropyl E-13 4-pyridyl methyl nitro CH.sub.2      CH.sub.2 n-butyl E-14 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2      n-butyl n.sub.D.sup.20 1.5820 E-15 4-isothiazolyl H nitro CH.sub.2      CH.sub.2 n-butyl E-16 3-methyl-5-isooxazolyl H nitro CH.sub.2 CH.sub.2      sec-butyl E-17 4-pyridazinyl H nitro (CH.sub.2).sub.3 sec-butyl E-18      2-chloro-5-pyridyl H nitro CH.sub.2       CH.sub.2 n-hexyl E-19 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2      difluoromethyl E-20 2-fluoro-5-thiazolyl H nitro (CH.sub.2).sub.3      difluoromethyl E-21 3-methyl-6-pyridazinyl H nitro CH.sub.2 CH.sub.2      trifluoromethyl       E-22 2-fluoro-5-pyridyl H nitro      ##STR53##       2-chloroethyl  E-23 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2      2-chloroethyl E-24 2-chloro-5-thiazolyl H nitro (CH.sub.2).sub.3      2-chloroethyl E-25 2-fluoro-5-oxazolyl H nitro CH.sub.2 CH.sub.2      2,2,2-trifluoroethyl E-26 2-bromo-5-pyridyl H cyano CH.sub.2 CH.sub.2      3-chloropropyl E-27 3-pyridyl H nitro CH.sub.2 CH.sub.2 cyclohexylmethyl      E-28 2-fluoro-5-pyridyl H nitro CH.sub.2 CH.sub.2 cyclopropylmethyl E-29      1,2,3-triadiazol-5-yl H nitro CH.sub.2 CH.sub.2 cyclopentyl E-30a      2-chloro-5-pyridyl methyl nitro CH.sub.2 CH.sub.2 methoxymethyl  E-30b      2-chloro-5-pyridyl H cyano       ##STR54##       2-(3-trifluoro-methylphenoxy)ethyl mp. 82-85° C.       E-31a 2-methyl-5-pyridyl H nitro CH.sub.2 CH.sub.2 2-phenoxyethyl E-31b      2-chloro-5-triazolyl H nitro CH.sub.2       CH.sub.2 2-(2,4-dichloro-5-pyridyloxy)ethyl mp. 77-80° C. E-32      2-trifluoromethyl-5-thiazolyl H nitro (CH.sub.2).sub.3 4-chlorophenoxy-me      thyl E-33 3-chloro-6-pyridazinyl H cyano CH.sub.2 CH.sub.2 ethoxymethyl      E-34 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2 3-methylthiopropyl      n.sub.D.sup.20 1.6067       E-35 2-chloro-5-pyridyl H nitro      ##STR55##       methylthiomethyl       E-36 2-trifluoromethyl-5-thiazolyl H nitro (CH.sub.2).sub.3 isopropylthi      omethyl E-37 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2 hydroxymethyl      E-38 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2 2-hydroxyethyl E-39      2-chloro-5-thiazolyl H cyano (CH.sub.2).sub.3 3-hydroxypropyl E-40      2-chloro-5-pyridyl H nitro CH.sub.2       CH.sub.2 2,2,2-trichloro-1-hydroxyethyl E-41 2-chloro-5-pyridyl H nitro C      H.sub.2 CH.sub.2 2-acetyloxyethyl E-42 2-bromo-5-pyridyl H nitro      CH.sub.2       CH.sub.2 2-(O,Odiethylthiophosphonothio)ethyl E-43 1,2,5-thiaziazol-3-yl       H nitro CH.sub.2 CH.sub.2 thiocyanatomethyl E-44 2-chloro-5-pyridyl H      nitro CH.sub.2 CH.sub.2 2-thiocyanatoethyl E-45 2,4-dichloro-5-thiazolyl      H nitro CH.sub.2 CH.sub.2 2-thiocyanatoethyl E-46 5-oxazolyl H nitro      CH.sub.2 CH.sub.2 2-ethylsulfonylethyl E-47a 2-difluoromethyl-5-pyridyl      H nitro CH.sub.2 CH.sub.2 cyanomethyl E-47b 2-chloro-5-pyridyl H nitro      CH.sub.2 CH.sub.2 cyanomethyl mp. 120-121°       C. E-48 2-chloro-5-pyridyl H cyano CH.sub.2 CH.sub.2 cyanomethyl      n.sub.D.sup.20 1.6015 E-49 3-methyl-5-isooxazolyl H nitro CH.sub.2      CH.sub.2 1-cyanoethyl E-50 2-chloro-5-pyridyl methyl nitro CH.sub.2      CH.sub.2 2-dimethylamino-ethyl E-51 2-fluoro-5-thiazolyl H nitro      CH.sub.2 CH.sub.2 trimethylsilylethyl  E-52 2-chloro-5-pyridyl methyl      nitro       ##STR56##       benzyl  E-53a 2-chloro-5-pyridyl H cyano CH.sub.2       CH.sub.2 4-chlorobenzyl mp. 161-163° C. E-53b 2-fluoro-5-pyridyl      H nitro CH.sub.2       CH.sub.2 4-tert-butyl-benzyl E-54 2-trifluoromethyl-5-oxazolyl H nitro      (CH.sub.2).sub.3 3-trifluoromethyl-benzyl E-55 2-trifluoromethyl-5-pyridy      l H nitro CH.sub.2       CH.sub.2 4-chlorobenzoylmethyl E-56 2-chloro-5-pyridyl H nitro CH.sub.2      CH.sub.2 1-(ethoxycarbonyl)-ethyl n.sub.D.sup.20 1.569 E-57 2-chloro-5-py      ridyl H cyano CH.sub.2       CH.sub.2  1-(ethoxycarbonyl)-ethyl E-58 2-methyl-5-pyridyl H nitro      CH.sub.2       CH.sub.2 m-tolyloxycarbonylmethyl E-59a 2-difluoromethyl-5-thiazolyl H      nitro (CH.sub.2).sub.3 3,3-dimethyl-2-butanon-1-yl E-59b 2-chloro-5-pyrid      yl H nitro CH.sub.2       CH.sub.2 3,3-dimethyl-2-butanon-1-yl mp. 105-110° C. E-60      1-isopropyl-4-pyrazolyl H nitro CH.sub.2       CH.sub.2 2-pyridylcarbonylmethyl E-61 2-trifluoromethylthio-5-pyridyl H      nitro CH.sub.2       CH.sub.2 Nmethylanilinocarbonylmethyl E-62 2-chloro-5-pyridyl H nitro      CH.sub.2 CH.sub.2 2-oxy-1,3-dioxan-4-yl E-63a 4-isooxazolyl H cyano      (CH.sub.2).sub.3 2-oxolanylmethyl E-63b 2-chloro-5-pyridyl H nitro      CH.sub.2 CH.sub.2 1-(dimethylaminocarbonyl)ethyl mp. 150-153° C.      E-64 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2 2-oxo-3-methyl-      1,3-thiazolidin-      5-yl-methyl E-65 2-fluoro-5-pyridyl H nitro      CH.sub.2 CH.sub.2 3-quinolinyl E-66 2-bromo-5-pyridyl H nitro CH.sub.2      CH.sub.2 2-chloro-6-benzothiazolyl E-67 2-chloro-5-thiazolyl H nitro      (CH.sub.2).sub.3 5,6-dichloro-2-benzothiazolyl E-68a 4-isothiazolyl H      nitro CH.sub.2 CH.sub.2 phenethyl E-68b 2-chloro-5-pyridyl H nitro      CH.sub.2       CH.sub.2 2-chloro-6-pyridyl n.sub.D.sup.50 1.6117 E-69 3-trifluoromethyl      -5-iso-oxazolyl H nitro (CH.sub.2).sub.3 6-quinoxalinyl E-70 2-chloro-5-p      yridyl H nitro CH.sub. 2 CH.sub.2 phenyl E-71a 2-chloro-5-thiazolyl H      cyano CH.sub.2 CH.sub.2 4-nitrophenyl E-71b 2-chloro-5-pyridyl H nitro      CH.sub.2 CH.sub.2 3,5-dichloro-2-pyridyl mp. 203-205° C. E-72      2-chloro-5-pyrimidinyl H nitro CH.sub.2 CH.sub.2 3,5-dichloro-2-pyridyl      E-73 1-methyl-4-imidazolylmethyl H nitro (CH.sub.2).sub.3 4,5-dichloro-2-      thiazolyl E-74 4-pyridazinyl methyl nitro CH.sub.2       CH.sub.2 2-benzoxazolyl E-75 2-chloro-5-pyridyl H nitro CH.sub.2      CH.sub.2 allyl mp. 103-105° C. E-76a 3-chloro-5-oxazolyl H nitro      CH.sub.2 CH.sub.2 3-chloroallyl E-76b 2-chloro-5-pyridyl H nitro      CH.sub.2       CH.sub.2 3-chloroallyl n.sub.D.sup.20 1.6095 E-77a 2,3-difluoro-5-pyridy      l H nitro CH.sub.2 CH.sub.2 propargyl E-77b 3-methyl-5-isooxazolyl H      cyano (CH.sub.2).sub.3 propargyl n.sub.D.sup.20 1.5667 E-78a 2-chloro-5-p      yridyl H cyano CH.sub.2 CH.sub.2 methoxy E-78b 2-fluoro-5-thiazolyl H      cyano CH.sub.2 CH.sub.2 3-chloroallyl E-79 2-chloro-5-pyrazyl H nitro      CH.sub.2       CH.sub.2 benzyloxy E-80 2-fluoro-5-pyridyl H nitro (CH.sub.2).sub.3      dichloro-fluoromethyl-thio E-81 2-chloro-5-pyridyl H nitro CH.sub.2      CH.sub.2 p-tolylthio E-82 2-bromo-5-pyridyl H nitro CH.sub.2 CH.sub.2      formyl E-83 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2 acetyl mp.      144.5-146° C. E-84 2-chloro-5-pyridyl H cyano CH.sub.2 CH.sub.2      acetyl n.sub.D.sup.20 1.5895 E-85 2-chloro-5-pyridyl H nitro CH.sub.2      CH.sub.2 trifluoroacetyl E-86 2-chloro-5-pyridyl H cyano CH.sub.2      CH.sub.2 chloroacetyl mp. 53-55° C.  E-87 2-chloro-5-pyridyl H      nitro       ##STR57##       trichloroacetyl  E-88 1,2,5-oxadiazol-3-yl H nitro (CH.sub.2).sub.3      2,2-difluoropropionyl       E-89a 2-chloro-5-pyridyl H nitro      ##STR58##       chloroacetyl  E-89b 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2      bromoacetyl mp. 200-203° C. (decomp.) E-90 2-chloro-5-thiazolyl H      nitro CH.sub.2 CH.sub.2 1,1-dichloro-2,2-dimethylcyclopropylcarbonyl      E-91 3-methyl-5-isooxazolyl H nitro CH.sub.2 CH.sub.2 acetyl mp.      134-136° C. E-92a 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2      butyryl mp. 137-140° C. E-92b 2-chloro-5-pyridyl H nitro CH.sub.2      CH.sub.2 valeryl E-93 5-thiazolyl H nitro (CH.sub.2).sub.3 trichloroacryl      oyl E-94 1,2,5-thiadiazol-3-yl H cyano CH.sub.2 CH.sub.2 methoxyacetyl      E-95 5-pyrimidinyl H nitro CH.sub.2       CH.sub.2 cyanoacetyl E-96 2-fluoro-5-pyridyl H nitro CH.sub.2 CH.sub.2      4-chlorobenzoyl mp. 149-152° C. E-97a 2-chloro-5-pyridyl H cyano      CH.sub.2 CH.sub.2 benzoyl mp. 158-161° C. E-97b 2-bromo-5-pyridyl      H nitro CH.sub.2       CH.sub.2 2,6-difluorobenzoyl E-98 2-fluoromethyl-5-pyridyl H nitro      CH.sub.2 CH.sub.2 2-trifluoromethyl-benzoyl E-99a 3-pyridyl H cyano      CH.sub.2 CH.sub.2 2-fluoromethoxy-benzoyl E-99b 2-chloro-5-thiazolyl H      nitro (CH.sub.2).sub.3 3-methylbenzoyl mp. 146-148.5°       C. (decomp.) E-100 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2      2,4-dichloro-5-thiazolylcarbonyl E-101 2-chloro-5-pyridyl H nitro      CH.sub.2       CH.sub.2 5-methyl-2-pyrimidinylcarbonyl E-102 2-chloro-5-pyridyl H      nitro CH.sub.2       CH.sub.2 3-methyl-1,4-oxazin-2-yl-carbonyl E-103 1-ethyl-4-pyrazolyl      methyl nitro (CH.sub.2).sub.3 5-nitro-2-furoyl E-104 4-isothiazolyl H      nitro (CH.sub.2).sub.3 2-naphthoyl E-105 2-methyl-5-thiazolyl H nitro      CH.sub.2 CH.sub.2 4,6-dichloro-1,3,5-triazin-2-yl-carbonyl E-106a      2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2 2,4-dichloro-m-toluoyl      E-106b 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2 2-furoyl mp.      162-163° C. E-107 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2      2-chloro-5-pyridylcarbonyl mp. 118-122°       C. E-108 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2 ethoxycarbonyl      mp. 125-126° C. E-109 2-chloro-5-pyridyl H cyano CH.sub.2      CH.sub.2 ethoxycarbonyl n.sub.D.sup.20 1.5880 E-110 2-methyl-5-pyridyl      methyl nitro CH.sub.2       CH.sub.2 2-methoxyethoxycarbonyl E-111 2-methyl-5-pyrazinyl H nitro      CH.sub.2 CH.sub.2 3-bromopropoxycarbonyl E-112 2-chloro-5-pyridyl H      cyano (CH.sub.2).sub.3 n-hexyloxycarbonyl E-113 2-chloro-5-thiazolyl H      nitro CH.sub.2 CH.sub.2 benzyloxycarbonyl E-114a 2-chloro-5-pyridyl H      nitro CH.sub.2 CH.sub.2 phenoxycarbonyl mp. 135-140° C. E-114b      2-chloro-5-pyridyl H nitro CH.sub.2       CH.sub.2 benzyloxycarbonyl n.sub.D.sup.50 1.5986 E-115 2-chloro-5-pyridy      l H nitro CH.sub.2 CH.sub.2 3,5,6-trichloro-2-pyridyl E-116 4-pyridyl      methyl nitro CH.sub.2       CH.sub.2 isopropylthiocarbonyl E-117 1-methyl-4-pyrazolyl H nitro      (CH.sub.2).sub.3 phenylthiocarbonyl E-118 2-chloro-5-pyridyl H nitro      CH.sub.2 CH.sub.2 methylaminocarbonyl E-119 2-chloro-5-pyridyl H nitro      CH.sub.2 CH.sub.2 3-chloroanilinocarbonyl mp. 120-123° C. E-120      2-chloro-5-thiazolyl H cyano CH.sub.2 CH.sub.2 allylaminocarbonyl E-121      2-bromo-5-pyridyl H nitro CH.sub.2 CH.sub.2 propargylaminocarbonyl E-122      2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2 dimethylaminocarbonyl mp.      186-188° C. E-123 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2      diethylaminocarbonyl E-124 3-pyridyl H nitro (CH.sub.2).sub.3 2-methylpip      eridinocarbonyl E-125 2-fluoro-5-pyrimidinyl H nitro CH.sub.2 CH.sub.2      Nmethylanilinocarbonyl E-126 2-chloro-5-pyridyl H nitro CH.sub.2      CH.sub.2 methylsulfonyl mp. 191-192° C. E-127 5-chloro-2-pyridyl      H nitro CH.sub.2 CH.sub.2 chloromethylsulfonyl E-128 2-chloro-5-pyridyl      H cyano CH.sub.2 CH.sub.2 tosyl E-129 3-methyl-5-isooxazolyl H nitro      CH.sub.2 CH.sub.2 methylsulfonyl mp. 156-158°       C. E-130 3-methyl-5-isooxazolyl H nitro CH.sub.2       CH.sub.2 2-methyl-5-nitro-phenylsulfonyl mp. 154-156° C. E-131      2-fluoro-5-pyridyl H nitro CH.sub.2 CH.sub.2 methoxysulfonyl E-132      2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2 dimethylaminosulfonyl E-133      2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2 O,Odimethylphosphono      n.sub.D.sup.24 1.5760 E-134 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2      Oethyl-Spropylthio-phosphono n.sub.D.sup.20 1.5615 E-135 1-methyl-4-pyraz      olyl H cyano (CH.sub.2).sub.3 Oethyl-Spropyl-dithiophosphono E-136      2-chloro-5-thiazolyl H nitro CH.sub.2       CH.sub.2 2-cyanoethyl n.sub.D.sup.20 1.6176 E-137 2-chloro-5-pyridyl H      cyano CH.sub.2 CH.sub.2 3,3-dimethyl-2-butanon-1-yl n.sub.D.sup.20      1.5446 E-138 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2 cyano E-139      2-chloro-5-thiazolyl H nitro CH.sub.2 CH.sub.2 methoxy-carbonyl mp.      122-126° C.  E-140 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2       ##STR59##       mp. 176-180° C. (decomp.)  E-141 2-chloro-5-pyridyl H nitro      CH.sub.2       CH.sub.2      ##STR60##       mp. 128-131° C.  E-142 2-chloro-5-pyridyl H nitro CH.sub.2      CH.sub.2 cyano mp. 85-87° C. E-143 2-chloro-5-pyridyl H nitro      CH.sub.2 CH.sub.2  chloroacetyl mp. 134-136°       C. E-144 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2 pivaloyl mp.      186-187° C. E-145 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2      3-cyanobenzyl mp. 154-158° C. E-146 2-chloro-5-pyridyl H nitro      CH.sub.2 CH.sub.2 pentafluorobenzyl mp. 166-170° C. E-147      2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2 pentafluorobenzoyl mp.      168-169° C.  E-148 2-chloro-5-pyridyl H nitro CH.sub.2 CH.sub.2       ##STR61##       mp. 181-185° C.  E-149 2-chloro-5-pyridyl H nitro CH.sub.2      CH.sub.2       ##STR62##       n.sub.D.sup.20 1.5880  E-150 2-chloro-5-pyridyl H nitro CH.sub.2      CH.sub.2 ethoxycarbonylmethyl mp. 148-151°       C. E-151 2-chloro-5-pyridyl H cyano CH.sub.2 CH.sub.2 cyano mp.      133-134° C. E-152 2-chloro-5-thiazolyl H nitro CH.sub.2 CH.sub.2      cyano n.sub.D.sup.20  1.6176

Example 6 (biological test)

Test on organophosphate-resistant green rice leafhoppers (Nephotettix cincticeps):

Preparation of a test chemical

Solvent: 3 parts by weight of xylene

Emulsifier: 1 part by weight of polyoxyethylene alkylphenyl ether

To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent and the stated amount of emulsifier, and the mixture was diluted with water to a predetermined concentration.

Testing method

A water dilution of each of the active compounds in a predetermined concentration prepared as above was sprayed onto rice plants, about 10 cm tall, grown in pots having a diameter of 12 cm at a rate of 10 ml per pot. The sprayed chemical was dried, and a wire net having a diameter of 7 cm and a height of 14 cm was put over each of the pots, and 30 female imagoes of rice leafhopper (Nephotettix cincticeps) of a strain having resistance to organophosphate chemicals were released into the net. The pots were placed in a constant-temperature chamber. Two days later, the number of dead insects was examined, and the kill ratio was calculated.

Example 7 (biological test)

Test on organophosphate-resistant white-backed planthopper (Sogattella furcifera):

Testing method

A water dilution of each of the active compounds in a predetermined concentration prepared as in the preceding Example was sprayed onto rice plants, 10 cm tall, grown in pots having a diameter of 12 cm at a rate of 10 ml per pot. The sprayed chemical was dried, and a wire net having a diameter of 7 cm and a height of 14 cm was put over each of the pots, and 30 female imagoes of white-backed planthopper (Sogatella furcifera) of a strain having resistance to organophosphate chemicals were released into the net and the pots were placed in a constant temperature chamber. Two days later, the number of dead insects was examined, and the kill ratio was calculated.

Results:

In the biological tests mentioned above (Examples 6 and 7) it has been found that the active compounds, shown in Table 2, have an excellent insecticidal effect at a concentration of 200 ppm, and also have a good insecticidal effect even in a concentration lower than 200 ppm.

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention. 

What is claimed is:
 1. A compound selected from the group consisting of1-cyclopropyl-2-nitroiminoimidazolidine of the formula: ##STR63## 1-(2-chloroethyl)-2-nitroiminoimidazolidine of the formula: ##STR64## 1-[2-(4-chlorophenoxy)ethyl]-2-nitroiminoimidazolidine of the formula: ##STR65## 1-(3-methylthiopropyl)-2-nitroiminoimidazolidine of the formula: ##STR66## 1-(2-cyanoethyl)-2-nitroiminoimidazolidine of the formula: ##STR67## 1-(3-cyanopropyl)-2-cyanoiminoimidazolidine of the formula: ##STR68## 1-(3,3-dimethyl-2-butanon-1-yl)-2-cyanoiminoimidazolidine of the formula: ##STR69## 1-(3,3-dimethyl-2-butanon-1-yl)-2-nitroiminoimidazolidine of the formula: ##STR70## 2-nitroimino-1-(3-pyridylcarbonylmethyl)imidazolidine of the formula: ##STR71## 2-cyanoimino-1-ethoxycarbonylmethyltetrahydropyrimidine of the formula: ##STR72## 1-[2-(O-ethyl-S-propylthiophosphonoxy)ethyl]-2-nitroiminoimidazolidine of the formula: ##STR73## 2-nitroimino-1-trimethylsilylmethylimidazolidine of the formula: ##STR74## 2-nitroimino-1-(2-thiazolyl)imidazolidine of the formula: ##STR75## 2-nitroimino-1-propylcarbonylimidazolidine of the formula: ##STR76## 2-cyanoimino-1-cyclopropylcarbonyltetrahydropyrimidine of the formula: ##STR77## 1-bromoacetyl-2-nitroiminoimidazolidine of the formula: ##STR78## 2-cyanoimino-1-trichloroacryloylimidazolidine of the formula: ##STR79## 1-(2-methoxyethoxycarbonyl)-2-nitroiminoimidazolidine of the formula: ##STR80## 1-benzyloxycarbonyl-2-nitroiminoimidazolidine of the formula: ##STR81## 1-ethylaminocarbonyl-2-nitroiminoimidazolidine of the formula: ##STR82## 1-dimethylaminocarbonyl-2-nitroiminoimidazolidine of the formula: ##STR83## 1-methylsulfonyl-2-nitroiminoimidazolidine of the formula: ##STR84## 2-nitroimino-1-phenylsulfonyltetrahydropyrimidine of the formula: ##STR85## 1-(O,O-dimethylphosphono)-2-nitroiminoimidazolidine of the formula: ##STR86## 1-(O-ethyl-S-propylthiophosphono)-2-nitroiminoimidazolidine of the formula: ##STR87## 1-(2,4-dichlorobenzoyl)-2-nitroiminoimidazolidine of the formula: ##STR88## 1-(3,5-dichlorobenzoyl)-2-cyanoiminoimidazolidine of the formula: ##STR89## 1-(2-furoyl)-2-nitroiminoimidazolidine of the formula: ##STR90##
 2. 1-(4-Nitrophenyl)-2-nitroiminoimidazolidine of the formula ##STR91## 